Ester of methacrylic acid



Patented Sept. 13, 1938 UNITED STATES 2,129,668 PATENT OFFICE ESTER. or nrnrmcnmc ACID Harold J. Barrett and Daniel E. Strain, Wilmington, DeL, assignors to E. I. du Pont de Nemours a Company, Wilmington, Del., a corporation 1 of Delaware No Drawing.

8 Claims.

The present invention relates to a new material, to methods for its preparation, and more particularly to isobutyl methacrylate and a process for its preparation. I

An object of the presentinventio'n is to provide a new composition of matter and a process for its preparation. A further object of the invention is to provide a new polymerizable composition of matter together with a process for its polymerization. A still further object of the invention is to provide a process for the preparation of. a methacrylic acid ester of isobutyl alcohol,

' which may beobtained by the ester interchange method of interacting the methyl ester of methacrylic acid with isobutanol. Another object is to provide a methacrylic acid ester of isobutanol. Another object of the invention is to provide mixtures or interpolymers of isobutyl methacryla'te The following specific example is furnished to illustrate a method of preparing the new composition of matter, but it will be understood that the invention is not limited to the details therein given.

Example 1.--296 parts of isobutanol were mixed with 1600 parts of methyl methacrylate, 9.4 parts of concentrated sulfuric acid and 96 parts of hydroquinone (all parts are given by weight) and the resulting mixture. heated on the water bath until solution was complete. The solution was then heated on an oil bath, held for approximately 6 hours ata temperature of approximately 150- C. under a 48" fractionating column fitted with a condenser arranged for controlling reflux. Distillate was collected at such a rate that the temperature at the head of the column remained at the boiling point of the methanolmethyl methacrylate binary (64). The cold'reaction mixture was neutralized and then washed and dried over a suitable desiccating medium,

the preparation of isobutyl methacrylate such,

for example, as are disclosed in our copending applicatlons'ser. Nos. 735,274-56-789 or The solvents were I Application February 19, 1935,

Serial No. 7,220

by any of the well known suitable esterification or ester interchange processes.

Isobutyl methacrylate is a mobile liquid as produced, is monomeric, and may be polymerized,

"according to the invention, by means of heat,

light, and/or a catalyst, e. g. as described for the polymerization of organic vinyl esters in Br. specification 15271/1914. Preferably a catalyst such as oxygen, ozone, an organic peroxide, an ozonide, etcL'is employed. Other catalysts which may be used include aluminum sulfate, boron fluoride, the mineral acids, e. g. hydrochloric and sulfuric acids, as well as the organic acids and more particularly acetic and methacrylic acids,etc., as well as the anhydrides and acid halides of such organic acids; metal salts of fatty acids and resinic acids, e. g. cobalt linoleate and resinate, manganese oleate and resinate, etc. The polymerization may be effected in the presence or absence of a solvent for both monomer and polymer, or in the presence of a solvent for the monomer and a non-solvent for the polymer,

or the monomer may be emulsified and then polymerized. Preferably polymerization is carried out at a moderate temperature, i. e. between 60-100 C., altho higher temperatures may be employed. The polymerization reaction is strongly exothermic and it may be necessary to control the temperature by cooling devices; the polymerization may be carried out in apparatus which may or niay not be provided with condensing devices, or in suitable pressure equipment.

As indicated, various polymerization methods may be employed and it has been found that the properties of the polymers, the physical properties to a. large extent and the chemical properties to a lesser extent, are altered considerably by the type of polymerizing process-utilized. The process described in the co-pending applications of Daniel E. Strain, Ser. Nos. 668,080 filed April 26, 1933, and 704,753 filed Dec. 30, 1933, maybe used, if desired.

Methods illustrating the polymerization of the monomeric ester will now be described, but it willbe understood that other suitable polymerizing processes may be employed.

Example 2.--102 parts (parts are given by weight) of isobutyl methacrylate monomer were dissolved in 275 parts of methanol in 'a bottle provided with a stopper, then. 1.0 parts of powdered benzoyl peroxide was added to this solution. After the benzoyl peroxide had all dissolved, 105 parts of water (an amount insufficient to cause permanent turbidity) were added. The bottle was securely closed and placed in an oven at approximately 65 C. After the polymerization was complete in approximately 72 hours, the mixture was allowed to cool. Theliquid was decanted from the polymer which had settled to the bottom. The polymer was removed from the cosity of 0.0a? poise. It is compatible withnitrocellulose.

The compatibility was determined by dissolving an equal volume of a 50% toluene solution of the polymerized-ester in a solution consisting of parts of nitrocellulose and 380 parts of butyl acetate. The resulting solution, when spread on a. glass plate and allowed to dry at room temperature, gave a clear transparent film.

The isobutyl methacrylate polymer was placed in a disk shaped mold in which it was subjected to a temperature of 92 C., and a. pressure of approximately 4000 pounds per square inch for approximately 15 minutes.

slightly brittle molded disk was obtained which softened at a temperature of 70 C.

A water-clear Example 3.400 parts of isobutyl methacrylate monomer and 8 parts of benzoyl peroxide were dissolved in 1600 parts of toluene. The resulting mixture was heated to a temperature of approximately 100 C. on a steam bath for 8 hours whereupon a clear, slightly yellow solution was obtained. From this solution there was obtained on precipitation with methanol a 69% yield of slightly yellow resinous polymer. The. resin is soluble in toluene and gasoline, insoluble in methanol, and has a viscosity of 0.08 poise (15% solution in toluene at C.)

Valuable products may be obtained by utilizing the polymer together with other polymeric compounds, particularly polymeric acrylic and methacrylic acid esters. Especially valuable products result if the monomeric esters are mixed prior to their polymerization; by this method interpolymers having a wide range of characteristics are possible. But to the unique characteristics of methyl methacrylate polymer, which is a hard resin having a high melting point, its admixture with the polymeric isobutyl methacrylate or interpolymers thereof are particularly well adapted for many uses.

The polymeric isobutyl ester of methacryllc acid is particularly well suited for thermoplastic molding as well as are many of its mixtures and interpolymers with other acrylic and methacrylic acid resins. The ester may be polymerized and/or preformed prior to placing in the mold and then may be moldedin accord with the usual procedural steps employed particularly in the molding of methyl methacrylate as described in the Rowland Hill copending application Ser. No. 641,113. The mold preferably is hot, prior to the introduction of the polymerization product, is then closed and the material so confined heated and pressed, the temperatures ranging from approximately 80-150 C., and pressures from 200 pounds per square inch, upward, are usually sufficient to give a suitably molded product. The presence or absence of plasticizers will, of course, alter considerably the molding conditions, and it is usually advantageous to have present plasticizers to alter the physical characteristics of the resulting product to fit the particular need for which the molded article is to be used.

The masses resulting from polymerization can immediately (i. e. in the state they have been obtained) be made into useful articles. It is possible to obtain the required articles if, for instance, the polymerization be carried out while the initial material is in a suitable mold, for

instance, one of steel or suitable metal, so that the articles, for example, umbrella handles, fountain pen barrels, buttons, and the like, are obtained directly from the mold. Or, if desired, the masses may be worked to the required shape by softening with suitable softeners or plasticizers in the presence of volatile solvents and,

after shaping, evaporating the solvent.

The polymerization products may be worked into the required shapes in various ways, for example, they can be softened and kneaded, rolled, compressed, drawn into wires, threads or the like, or the masses can be mixed with additional substance, nd rolled into plates, or films, or they may be pressed into the required shapes such as buttons, 'combs;.and the like.

The solid masses can'be worked by cutting, sawing, filing, or" the like, whether they be obtained directly by polymerization, or after special treatment of the polymerized masses. These shaped articles may be polished, and parts connected together by smearing the faces to be connected with a suitable solvent, such as acetone, butyl acetate, or the corresponding methacrylic acid ester.

The polymerization product dissolved in a suitable solvent which may or may not be the monomer may be transformed into a useful article, e. g., films and fibers, by casting and then evaporating the solvent, or by extrudingthru a suitable orifice into a precipitating bath or drying atmosphere. The polymer may be recovered from such solutions by precipitation with a; suitable non-solvent for the polymer.

The properties of the resulting masses may be widely varied by modification with plasticizers,

e. g. dibutyl phthalate, tricresyl phosphate, etc.,,

drying, semi-drying and non-drying oils, synthetic and natural resins, waxes, bitumens, cellulose derivatives, e. g. cellulose nitrate and ethyl cellulose, etc., pigments, fillers, and dyes, etc. Thus, it is possible to produce instead of hard glass-like masses, also soft and flexible masses; likewise, by the addition of suitable coloring means, it is possible to produce masses, or objects, having any desired color eifects. The incorporation of the additions can be effected either before, or during, the polymerizing process, or the additions can be made to the already formed polymerization products in a suitable condition.

If the polymerization of the isobutyl methacrylate be carried out in an incomplete manner, a syrupy solution of the polymerization product containing some unchanged monomer is obtained. This syrupy product can be utilized either directly, or along with other solvents, or diluents, for the production of substances to be used for coating, painting, or impregnating purposes. If, for instance, a porous substance such as wood, paper, textile fabric, artificial stone, or the like be coated with the said syrupy solution or be impregnated therewith, coatings and impregnations very resistant to wear are obtained on completing the polymerization of the coating, painting, or impregnation, for instance by exposing the article to artificial or natural light, or by heating it, or by employing both light and heat. In this case a portion of the unchanged ester in the syrupy solution may or may not be evaporated while another portion may be converted into the solid polymerization product. The articles thus treated have imparted to them a very high reslstance to external influences, e. g. resistance to water,- acids, alkalis, and atmospheric changes.

The said syrupy mass can be mixed with comminuted matter, such, for instance, as ground cork, of ground wood, fibrous substances, min-. eral fillers, or the like, and the mixture be made into the proper shape and while monomer present in the articles may be converted by suitable polymerization into the solid final product.

. It is also possible to start from solid, semisolid, or plastic polymerization products of the isobutyl methacrylate, these being softened by heating them by themselves, or with suitable solvents, and using them in their softened state. On cooling, or on the evaporation of the diluent, that may still be present, the products are converted into the solid form. A lacquer film may be prepared in this way.

Polymeric isobutyl methacrylate as well as mixtures 'and interpolymers with various polymerized acrylic and methacrylic acid esters can be used in suitable compositions for lacquering,

painting, or impregnating. The wholly or partly polymerized isobutyl ester, mixture of interpolymer containing it can be mixed with suitable additional substances to modify the properties of the lacquering, painting, or impregnating materials in any desired manner. As additions of this kind there may be mentioned oils (such, for

instance, as castor oil), dyes, powdered substances (such as zinc oxide), camphor, and other plasticizers, and the like.

In accordance with this invention it is possible to obtain valuable products if the said polymers be dissolved, or softened in suitable solvents and then be converted again to the solid state. The products thus obtained may be used for purposes for which cellulose esters have hitherto been used, namely, as substitutes for horn, amber, artificial resins, lacquers, for impregnation purposes, and also for the production of films, interlayers for safety glass, pressure adhesives, artificial threads, and the like.

The products thus formed have the advantage over products made fromnitrocellulose in being slower burning and odorless. By the addition of suitable agents, the strength and hardness of the products may be modified within wide limits so that it is possible to manufacture both hard, horn-like substances and soft and more pliable products. The products may also be modified by varying the conditions of the polymerization.

The monomer may be polymerized in the presence of a solvent and the solution used as such or the polymer recovered from the solution by evaporation or precipitation methods. In many cases, however, it is more profitable to use an amount of solvent insufllcient to produce a freely flowing solution, so that soft plastic masses are obtainedwhich can be pressed, kneaded, rolled, or drawn into shape, or formed into blocks, plates, or films.

Plasticizers or other modifying agents may be added to the monomer prior to polymerization or directly to the polymerized product, it being generally desirable to employ a plasticizer which is soluble in the polymer and the monomer, altho it is not essential that the dual solubility characterlstics be present. Thus, plasticizers or softening agents, such as, for example, camphor; phthalates, such as ethyl, propyl, isopropyl, butyl, isobutyli cyclohexyl, methyl cyclohexyl, or benzyl phthalate or phthalates of the mixed type, such as cyclohexyl butyl, benzyl butyl or butyl lauryl phthalate; esters of other dibasic acids, such as the ethyl, propyl', isopropyl, butyl, isobutyi, cyclohexyl, methyl cyclohexyl or benzyl esters of succinic, fumarlc, tartaric, adipic and sebacic acids; esters of monobasic acids, such as the butyl, isobutyi, cyclohexyl, methyl cyclohexyl, benzyl or lauryl esters of lauric, laevulinic, benzoic, benzoyl propionic and benzoyl benzoic acids;-esters of polyhydric alcohols, e. g. glycol and glycerol, such as glycol benzoate, glycol laevulinate, triacetin, tripropionin and tributyrin; the ether alcohol esters of the polycarboxylic acids, e. g. methoxy ethyl and ethoxy ethyl phihalate; substituted toluene sulphonamides,'such as ethyl paratoluene sulphonamide; substituted amides, such as tetraethyl phthalamide, tetrabutyl succinamide, tetrabutyl adipamide, tetraethyl phthalamide; hydrocarbons, such as dixylyl ethane; halogenated hydrocarbons, such as chlorinated diphenyls and dichlordibenzyl; ether compounds such as dicresoxy ethyl ether; and drying, non-drying or semidrying oils, such as castor oil, cottonseed oil, linseed oil, and the like. These additions also facilitate later mechanical treatment, as cutting, sawing, and polishing.

The polymerized isobutyl methacrylate ester, mixtures of the polymerized ester with other polymerizable compounds such as polymerizable compounds of methacrylic or acrylic acids, or vinyl compounds; or interpolymers of the esters with such other compounds, may be used advantageously as safety glass interlayers. These polymerized. esters, mixtures thereof, or interpolymers thereof may be plasticized or otherwise modified as desired. The compositions in an unpolymerized, partially polymerized, or completely polymerized condition may be used in laminated glass. If the composition is in the unpolymerized or partially polymerized state, polymerization may be effected by subjecting the composite to light and/or heat.

From a consideration of the above specification it will be realized that various changes may be made in the process or product without departing from the invention or sacrificing any of its advantages.

We claim:

1. A process for the polymerization of isobutyl methacrylate which comprises heating the monomeric ester dissolv'ed in methanol containing benzoyl peroxide and water to a temperature of approximately 65 C., and holding it at that temperature until polymerization is substantially complete. a I

2. A process for the polymerization of isobutyl methacrylate which comprises heating the monomeric isobutyl methacrylate in the presence of a polymerization catalyst to a temperature .between and 100 C., and holding the ester at that temperature until polymerization is substantially complete. A

3. The polymeric isobutyl methacrylate prepared in accord with the process of claim 2.

4. A molding composition comprising the polymeric isobutyl methacrylate obtained in accord with the process of claim 2.

5. A lacquer composition comprising the polymeric isobutyl methacrylate obtained in accord with the process of claim 2.

6. An interpolymer of isobutyl methacrylate and a polymerizable compound selected from the group consisting of vinyl compounds, methacrylic acid compounds and acrylic acid compounds, the monomeric compounds being polymerized in accord with the process of claim 2.

HAROLD J. BARRETT. DANIEL E. STRAIN. 

